Methylbutoxy-propionitriles and their use as perfumes

ABSTRACT

PCT No. PCT/EP93/03417 Sec. 371 Date Sep. 26, 1995 Sec. 102(e) Date Sep. 26, 1995 PCT Filed Dec. 2, 1993 PCT Pub. No. WO94/13626 PCT Pub. Date Jun. 23, 1994Novel compounds, 3-(2-methylbut-1-oxy)- and 3-(3-methylbut-1-oxy)-2-methylpropionitrile, use of these compounds as fragrance materials, and perfumes containing these compounds.

This application is a 371 of PCT/EP93/03417 filed Dec. 2, 1993 andpublished as WO94/13626 Jun. 23, 1994.

The present invention relates to certain methylbutoxypropionitriles, tothe use of these compounds as fragrance materials and to perfumes andperfumed products containing these compounds.

Many synthetic fragrance materials have been developed, especially inthe last decades to substitute known perfume materials of naturalorigin. Nevertheless there is a constant need for new syntheticfragrance materials which are more stable than those previouslydeveloped and/or have additional or more delicate odour notes to furthercomplete the fragrance palette from which the perfumer can chose incomposing perfumes which are suitable also for various aggressiveenvironments.

Various aliphatic and aromatic nitriles are known in the art ofperfumery. They were developed because of their good stability inaggressive media and their general odour similarity with thecorresponding aldehydes, many of which were already used in perfumerybefore the development of the nitriles. Various examples are describedin S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969).Certain ether-nitriles have been described in the art. They wereprepared by addition of aliphatic alcohols to acrylonitrile,methacrylonitrile or crotonnitrile. The ether-nitriles are reported tohave odours reminiscent of the alcohols from which they were prepared.Thus, J. Kulesza et al, Riechstoffe, Aromen, Korperpflegemittel. Nr.2/75, pages 34, 37 describe a series of addition products of alcohols toacrylonitrile. From the odour decriptions it is clear that the odours ofmost ether-nitriles are similar to those of the corresponding alcohols.Similarly, in DE-A-2601825 the addition products of various saturatedand unsaturated aliphatic alcohols to acrylonitrile have been describedas possibly of interest in perfumery and as polar solvents.

Although this reference gives very little information on the actualodours of the compounds, it does say that the odour is determined, atleast in part, by the corresponding alcohol. The odour of3-methylbut-3-en-1-oxy-propionitrile is decribed as mainly fruity,green. No further particulars or examples of any use of the compounds inperfumery are given. Finally, in EP-A-0 491 127 varioushexenyloxy-propionitriles and hexenyloxy-methylpropio-nitriles aredescribed as having predominantly green odour notes.

It has now been found that 3-(2-methylbut-1-oxy)- and3-(3-methylbut-1-oxy)-2-methylpropionitrile, of which the formulae arepresented below, are valuable fragrance materials with jasmine-typeodours with lactonic notes. ##STR1##

The olfactive properties of the compounds of the invention are thussurprisingly different from what might have been expected from the priorart in that they are not reminiscent of the corresponding alcohols,which both have a pungent and from a perfumery point of view uselessodour. Also, the olfactive properties of the compounds of the inventionare very different from those of the ether-nitriles of the prior art.

The ether-nitriles according to the invention are not only novel asperfume components, they are also novel as such. They may be preparedaccording to methods known in the art for similar compounds, such asdescribed by J. H. MacGregor and C. Pugh, J. Chem Soc., 535 [1945], oras decribed in DE-A-2 121 325, DE-A-2 217 494 or EP-A-0 491 127.

The ether-nitriles according to the invention are powerful fragrancematerials which may be used as such to impart, strengthen or improve ajasmine odour note in products, or they may be used as a component of aperfume to impart, strengthen or improve a jasmine note therein. For thepurposes of this invention a perfume is intended to mean a mixture offragrance materials, if desired mixed with or dissolved in a suitablesolvent or mixed with a solid substrate, which is used to impart adesired odour to the skin and/or all types of products. Examples Of suchproducts are: fabric washing powders and liquids and other fabric careproducts; detergents and household cleaning, scouring and disinfectionproducts; air fresheners, room sprays and pomanders; candles; soaps,shampoos and other personal cleaning products; cosmetics such as creams,ointments, toilet waters, preshave-, aftershave- and other lotions,talcum powders, body deodorants and antiperspirants.

Fragrance materials which can be advantageously combined with thecompounds according to the invention or the said organoleptic mixturesare, for example, natural products such as extracts, essential oils,absolutes, resinoids, resins, concretes etc., but also synthetic basicsubstances such as hydrocarbons, alcohols, aldehydes, ketones, ethers,acids, esters, acetals, ketals, nitriles, etc., including saturated andunsaturated compounds, aliphatic, carbocyclic and heterocycliccompounds.

Such fragrance materials are mentioned, for example, in S. Arctander,Perfume and Flavor Chemicals (Montclair, N.J., 1969), in S. Arctander,Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960)and in "Flavor and Fragrance Materials - 1991" Allured Publishing CoWheaton, Ill. USA.

Examples of fragrance materials which can be used in combination withthe ether-nitriles according to the invention are: geraniol, geranylacetate, linalol, linalyl acetate, tetrahydrolinalol, citronellol,citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate,tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate,2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate,benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate,dimethylbenzyl-carbinol, trichloromethylphenylcarbinyl acetate,p-tert-butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate,vetiverol, 3-hexylcinnamaldehyde,2-methyl-3-(p-tert-butylphenyl)propanal,2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert-butylphenyl)-propanal,tricyclodecenyl acetate, triclyclodecenyl propionate,4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexenecarbaldehyde,4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde,4-acetoxy-3-pentyltetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane,2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, n-decanal,n-dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehydedimethyl-acetal, phenylacetaldehyde diethylacetal, geranyl nitrile,citronellyl nitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedrylmethyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin,coumarin, eugenol, vanillin, diphenyl oxide, hydroxy-citronellal,ionones, methylionones, isomethylionones, irones, cis-3-hexenol andesters thereof, indan musks tetralin musks isochroman musks macrocyclicketones, macrolactone musks ethylene brassylate, aromatic nitromusks.

Solvents which can be used in perfume compositions which containcompounds according to the invention are, for example: ethanol,isopropanol, diethyleneglycol monoethyl ether, dipropylene glycol,diethyl phthalate, triethyl citrate, etc.

The quantities in which the ether-nitriles according to the inventioncan be used in perfumes or in products to be perfumed may vary withinwide limits and depend, inter alia, on the nature of the product, on thenature and the quantity of the other components of the perfume in whichthe compounds are used and on the olfactive effect desired. It istherefore only possible to specify wide limits, which, however, providesufficient information for the specialist in the art to be able to usethe ether-nitriles according to the invention for his specific purpose.In perfumes an amount of 0.01% by weight or more of the compoundsaccording to the invention will generally have a clearly perceptibleolfactive effect. Preferably the amount is 0.1% by weight and may be upto 80% by weight. The amount of ether-nitriles according to theinvention present in products will generally be at least 0.1 ppm byweight.

The following examples are only intended to illustrate the preparationand use of the ether-nitriles according to the invention, but theinvention is not in any way limited thereto

EXAMPLE 1 Preparation of ether-nitriles

The methylbutanol (0,34 mol) was put in a three-necked flask withpotassium hydroxide catalyst (1 g). The methacrylonitrile (0,20 mol) wasadded dropwise over half an hour, the reaction being carried out undernitrogen. After addition, the mixture was heated to 50° C. and allowedto reflux for 1 hour. Most of the excess alcohol was removed using therotary evaporator. The organic layer was extracted with cyclohexane (50ml) in a separating funnel and then washed with hydrochloric acid (0,5M,100 ml). The aqueous layer was run off and the remaining organic layerwas washed with a second portion of hydrochloric acid and then withbrine (100 ml). The organic layer was then dried over magnesiumsulphate. After filtering off the magnesium sulphate and washing thefilter paper with a little cyclohexane, the solvent was evaporated offusing a rotary evaporator. Distillation was carried out under reducedpressure, the unreacted alcohol being the first fraction obtained,followed by the ether-nitrile, obtained as a colourless oil.

GC was done on a Vista 6000 Gas Chromatograph, using a packed. SE52column, temperature programmed at 70°-240° C., rising 4° C./min.Retention times are given in minutes. ¹ H-NMR spectra were obtained inCDCL₃ as the solvent, using a Jeol GSX 400 MHz NMR spectrometer. TMS wasused as an internal standard. Chemical shifts are given in ppm as δvalues.

3-(2-Methylbut-1-oxy) -2-methylpropionitrile GC r.t.: 16.66; BP 78° C.at 0.01 kPa; ¹ H-NMR (400 MHz): 0.85 (m, 6H, 2Me), 1.15 (m, 1H), 1.3 (d,3H, MeCHCN), 1.4 (m, 1H), 1.65 (m, 1H), 2.8 (m, 1H), 3.25-3.45 (m, 4H,CH₂ OCH₂); Yield: 45%.

3-(3-Methylbut-1-oxy)-2-methylpropionitrile GC r.t.: 16.49; BP 60° C. at0.01 kPa; ¹ H-NMR (400 MHz): 0.87 (d, 6H, 2Me), 1,28 (d, 3H, MeCHCN),1,44 (q, 2H), 1,67 (m, 1H, MeCHME), 2.80 (m, 1H CHCN), 3.41-3.51 (m, 4H,CH₂ OCH₂); Yield: 60%.

EXAMPLE 2

A chypre-type perfume for use in toilet soap was prepared according tothe following recipe.

    ______________________________________                                        Bergamot oil             19,0                                                 Methyl ionone iso        12,0                                                 P-tert-butyl-dihydrocinnamic aldehyde                                                                  12,0                                                 Jasmin absolute          10,0                                                 Coumarin                 7,0                                                  Amyl salicylate          6,5                                                  Rosana extra A-118001 (Q)                                                                              5,0                                                  Vetiver Bourbon          5,0                                                  Ylang oil                4,5                                                  Musk ambrette sub. AB 2002 (Q)                                                                         4,0                                                  Patchouli oil acid washed                                                                              3,0                                                  Clove stem oil           3,0                                                  Undecalactone (10%)*     2,5                                                  Dodecanal (50%)*         1,0                                                  Treemoss absolute colourless                                                                           1,0                                                  Cervolide (Q)            1,0                                                  Civet AB 394A (Q)        0,5                                                  Dipropylene glycol       2,5                                                  3-(3-Methylbut-1-oxy)-2-methylpropionitrile                                                            0.5                                                  Total                    100                                                  ______________________________________                                         *solution in dipropylene glycol                                               (Q) fragrance material marketed by Quest International, Ashford, Kent,        U.K.                                                                     

3-(3-Methylbut-1-oxy)-2-methylpropionitrile supports and strengthens thefloral aspects of the above fragrance, in particular the Jasmin note.

I claim:
 1. 3-(2-methylbut-1-oxy)-2-methylpropionitrile or3-(3-methylbut-1-oxy)-2-methylpropionitrile.
 2. Perfumes containingether-nitriles characterized in that they contain one or both of3-(2-methylbut-1-oxy)-2-methylpropionitrile or3-(3-methylbut-1-oxy)-2-methylpropionitrile.
 3. Perfumes according toclaim 2 characterized in that they contain at least 0.01% by weight ofthe mentioned ether-nitriles.